JP4428019B2 - Method for producing water-soluble polyurethane - Google Patents
Method for producing water-soluble polyurethane Download PDFInfo
- Publication number
- JP4428019B2 JP4428019B2 JP2003365499A JP2003365499A JP4428019B2 JP 4428019 B2 JP4428019 B2 JP 4428019B2 JP 2003365499 A JP2003365499 A JP 2003365499A JP 2003365499 A JP2003365499 A JP 2003365499A JP 4428019 B2 JP4428019 B2 JP 4428019B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- water
- diisocyanate
- compound
- soluble polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920002635 polyurethane Polymers 0.000 title claims description 35
- 239000004814 polyurethane Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 150000002009 diols Chemical class 0.000 claims description 34
- 239000002270 dispersing agent Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 28
- -1 diisocyanate compound Chemical group 0.000 claims description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims description 23
- 229920005862 polyol Polymers 0.000 claims description 21
- 150000003077 polyols Chemical class 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 14
- 238000012674 dispersion polymerization Methods 0.000 claims description 14
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000005056 polyisocyanate Substances 0.000 claims description 13
- 229920001228 polyisocyanate Polymers 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 229920005906 polyester polyol Polymers 0.000 claims description 7
- 230000000873 masking effect Effects 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Chemical group 0.000 claims description 4
- 229920000180 alkyd Polymers 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 4
- 239000003759 ester based solvent Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005453 ketone based solvent Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 238000006243 chemical reaction Methods 0.000 description 42
- 238000003756 stirring Methods 0.000 description 23
- 229920005749 polyurethane resin Polymers 0.000 description 21
- 238000001125 extrusion Methods 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 16
- 229920001515 polyalkylene glycol Polymers 0.000 description 16
- 239000004570 mortar (masonry) Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 125000005442 diisocyanate group Chemical group 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 description 12
- 239000010425 asbestos Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 229910052895 riebeckite Inorganic materials 0.000 description 11
- 125000001165 hydrophobic group Chemical group 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920003086 cellulose ether Polymers 0.000 description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- MDZUBPKPKVUHNW-UHFFFAOYSA-N 1,15-diisocyanatopentadecane Chemical compound O=C=NCCCCCCCCCCCCCCCN=C=O MDZUBPKPKVUHNW-UHFFFAOYSA-N 0.000 description 1
- AJSKFBFHLYPSEM-UHFFFAOYSA-N 1,16-diisocyanatohexadecane Chemical compound O=C=NCCCCCCCCCCCCCCCCN=C=O AJSKFBFHLYPSEM-UHFFFAOYSA-N 0.000 description 1
- JCIIKRHCWVHVFF-UHFFFAOYSA-N 1,2,4-thiadiazol-5-amine;hydrochloride Chemical compound Cl.NC1=NC=NS1 JCIIKRHCWVHVFF-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- JFRQLKNEDLLXOQ-UHFFFAOYSA-N 1,3-diisocyanato-2,4-dimethylbenzene Chemical compound CC1=CC=C(N=C=O)C(C)=C1N=C=O JFRQLKNEDLLXOQ-UHFFFAOYSA-N 0.000 description 1
- BQHPNDYUVBBCQF-UHFFFAOYSA-N 1,3-diisocyanato-5-methylbenzene Chemical compound CC1=CC(N=C=O)=CC(N=C=O)=C1 BQHPNDYUVBBCQF-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- XCYAYYRYTNCXQL-UHFFFAOYSA-N 1,4-diisocyanato-2,5-dimethylbenzene Chemical compound CC1=CC(N=C=O)=C(C)C=C1N=C=O XCYAYYRYTNCXQL-UHFFFAOYSA-N 0.000 description 1
- DKBHJZFJCDOGOY-UHFFFAOYSA-N 1,4-diisocyanato-2-methylbenzene Chemical compound CC1=CC(N=C=O)=CC=C1N=C=O DKBHJZFJCDOGOY-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SIZPGZFVROGOIR-UHFFFAOYSA-N 1,4-diisocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=C(N=C=O)C2=C1 SIZPGZFVROGOIR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- UTFSEWQOIIZLRH-UHFFFAOYSA-N 1,7-diisocyanatoheptane Chemical compound O=C=NCCCCCCCN=C=O UTFSEWQOIIZLRH-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- RNQBCZCPNUHWLV-UHFFFAOYSA-N 1,8-dioxacyclotetradecane-2,7-dione Chemical compound O=C1CCCCC(=O)OCCCCCCO1 RNQBCZCPNUHWLV-UHFFFAOYSA-N 0.000 description 1
- FHGPADAQQRYSEH-UHFFFAOYSA-N 1-ethyl-2,4-diisocyanatobenzene Chemical compound CCC1=CC=C(N=C=O)C=C1N=C=O FHGPADAQQRYSEH-UHFFFAOYSA-N 0.000 description 1
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
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- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical compound CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
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- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
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- 150000002902 organometallic compounds Chemical class 0.000 description 1
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- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229940096826 phenylmercuric acetate Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
本発明は、セメント系材料押出成形用に用いられる水溶性ポリアルキレングリコールを主な原料とする、新規な高分子の製造法に関する。 The present invention relates to a novel method for producing a polymer using water-soluble polyalkylene glycol used for extrusion molding of a cement-based material as a main raw material.
従来からセメント、細骨材、繊維、水等からなるモルタルを真空押出成形機などで押出成形しセメント板等を製造する際に、押出中にモルタルから水を分離することなく成形するためには、水溶性の高分子をモルタルに添加する必要があった（例えば特許文献１）。 Conventionally, when manufacturing mortar made of cement, fine aggregate, fiber, water, etc. with a vacuum extrusion molding machine etc. to produce cement board etc., without molding water from mortar during extrusion, It was necessary to add a water-soluble polymer to the mortar (for example, Patent Document 1).
また押出直後の成形体の形状を保持するためには、モルタルが高いチクソ性を示すことが必要であるが、モルタルにメチルセルロースなどの水溶性高分子を添加するだけでは十分な保形性は得られなかった。そのため、従来は石綿（アスベスト）が水溶性セルロースエーテル類と併用されてきた（例えば特許文献１）。 In addition, in order to maintain the shape of the molded product immediately after extrusion, it is necessary that the mortar has high thixotropy. However, sufficient shape retention can be obtained only by adding a water-soluble polymer such as methylcellulose to the mortar. I couldn't. Therefore, conventionally, asbestos (asbestos) has been used in combination with water-soluble cellulose ethers (for example, Patent Document 1).
従って従来の押出成形では、水溶性セルロースエーテル類と石綿を併用することで、押出成形に必要なモルタルの保水性と保形性を満たしていたと言える。 Therefore, in conventional extrusion molding, it can be said that the water retention and shape retention of mortar necessary for extrusion molding were satisfied by using water-soluble cellulose ethers and asbestos together.
ところが、近年になって石綿の有害性が指摘され、押出成形においても石綿の使用は制限されるようになり、現在では石綿の代替物として、各種ポリマー繊維やガラス繊維などの石綿代替繊維類が用いられるようになってきた。しかしながら、これらの石綿代替繊維類を用いたモルタルは、石綿を用いたモルタルと比較して保形性に劣っていた。そのため、石綿代替繊維類を用いても、モルタルに保水性と同時に十分な保形性を付与しうる新規な押出成形助剤の開発が望まれていた。 However, in recent years, the harmfulness of asbestos has been pointed out, and the use of asbestos has also been limited in extrusion molding. Asbestos substitutes include asbestos substitute fibers such as various polymer fibers and glass fibers. It has come to be used. However, mortars using these asbestos substitute fibers were inferior in shape retention compared to mortars using asbestos. For this reason, there has been a demand for the development of a novel extrusion aid that can impart sufficient shape retention as well as water retention to mortar even when using asbestos substitute fibers.
また、水溶性セルロースエーテル類はモルタルの混練時に泡をかみ易く、泡により成形品の強度が低下し易いという問題があった。 In addition, water-soluble cellulose ethers have a problem that bubbles are easily formed during kneading of the mortar, and the strength of the molded product is easily lowered by the bubbles.
また、水溶性セルロースエーテル類は、原料に特定の天然パルプを用いる半合成高分子であるために比較的高価であり、押出成形品の原料コストを押し上げていた。またパルプの資源も限られており、より安価な工業原料から合成できる新しい押出成形助剤が待たれていた。 In addition, water-soluble cellulose ethers are relatively expensive because they are semi-synthetic polymers using a specific natural pulp as a raw material, and have increased the raw material cost of extruded products. Pulp resources are also limited, and new extrusion aids that can be synthesized from cheaper industrial raw materials have been awaited.
そこで、櫛形疎水基を有する高分子を用いた押出成形助剤が見出され、既に特許出願されている（例えば特許文献２、特許文献３）。 Thus, an extrusion aid using a polymer having a comb-shaped hydrophobic group has been found, and patent applications have already been filed (for example, Patent Document 2 and Patent Document 3).
櫛形疎水基を有する高分子は、水に容易に溶解させるために、粉末状であることが望まれる。しかし、櫛形疎水基を有する高分子は、押出機等の混練機や溶液あるいはバルク状で重合されるため、重合後に粉末状に塊砕あるいは加工する必要があった。しかし、櫛形疎水基を有する高分子は弾力性が高く、工業的に塊砕するには、凍結粉砕あるいは、タルクの混入後にジェットミル等で粉砕するしかないが、凍結粉砕法は、非常に高価であるし、タルクを混入すると、セメントの押出成形時に品質劣化を生じる。
他にポリウレタン系粉末重合物を得る方法として、非水溶媒中で原料を分散させながらポリウレタンを重合する非水分散重合法が知られている（例えば特許文献４、非特許文献１）。この方法は反応後、ろ過分離等により、容易に粉末樹脂を単離できるので経済的にも優れた方法である。原料の分散状態を維持するためには非水溶媒種の選択、または分散剤の添加により、分散状態を維持させることが可能である。しかし、既知の分散剤の場合、櫛形疎水基と同様なポリオレフィン部位を有しており、原料に対して５％以上と添加量が多量に必要であるため、重合して得られるポリウレタンの水溶性や押し出し成型助剤としての性能を損なう可能性が大いにあった（例えば特許文献５）。
As another method for obtaining a polyurethane-based powder polymer, a non-aqueous dispersion polymerization method is known in which polyurethane is polymerized while dispersing raw materials in a non-aqueous solvent (for example, Patent Document 4 and Non-Patent Document 1). This method is economically superior because the powder resin can be easily isolated after the reaction by filtration or the like. In order to maintain the dispersed state of the raw material, it is possible to maintain the dispersed state by selecting a non-aqueous solvent species or adding a dispersing agent. However, in the case of a known dispersant, it has the same polyolefin site as that of the comb-shaped hydrophobic group, and it is necessary to add 5% or more to the raw material in a large amount. There was a great possibility that the performance as an extrusion molding aid was impaired (for example, Patent Document 5).
水溶性セルロースエーテル類などの既存の押出成形助剤は、石綿を用いないセメント系材料の押出成形に用いるには保形性の点でまだ問題が残っていた。 Existing extrusion aids such as water-soluble cellulose ethers still have problems in terms of shape retention when used for extrusion of cement-based materials that do not use asbestos.
また、水溶性セルロースエーテル類はモルタルの混練時に泡をかみ易く、泡により成形品の強度が低下し易い並びに高価であるという問題があった。 In addition, water-soluble cellulose ethers have a problem in that foams tend to bite when kneading mortar, and the strength of the molded product tends to decrease due to the foams, and they are expensive.
これらの問題を解決するために発明された新規な押出成形助剤を開発したが、重合後に塊砕しなくてはならないという製造上の課題を残していた。 A novel extrusion aid was invented to solve these problems, but left the manufacturing problem of having to be crushed after polymerization.
従って本発明の目的は、より経済的でモルタルの保形性と成形品の強度に優れた新しい櫛形疎水基を有する高分子の製造法を提供することにある。 Accordingly, it is an object of the present invention to provide a method for producing a polymer having a new comb-shaped hydrophobic group which is more economical and has excellent mortar shape retention and excellent strength of a molded product.
本発明者らは上記の問題を解決すべく鋭意検討を重ねた結果、櫛形ジオールを会合基と
する新規な水溶性ポリウレタンを、プレポリマーを用いて不溶性溶媒中で分散重合する方法を開発した。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have developed a method for dispersing and polymerizing a novel water-soluble polyurethane having a comb-shaped diol as an associating group in an insoluble solvent using a prepolymer.
本発明は、化学式１（化１） The present invention is represented by Chemical Formula 1 (Chemical Formula 1)
ただし、ＡはＨＯ−Ａ−ＯＨが少なくとも両末端に水酸基を有しかつ数平均分子量が４００〜１００，０００の水溶性ポリオキシアルキレンポリオール（化合物Ａ）である２価基であり、該水溶性ポリオキシアルキレンポリオールが、エチレンオキサイドの重合物であり、ＢはＯＣＮ−Ｂ−ＮＣＯが全炭素数が（ＮＣＯ基の炭素を含めて）３〜１８のポリイソシアナート類よりなる群から選ばれたポリイソシアナート化合物（化合物Ｂ）である２価基であり、ＤはＨＯ−Ｄ−ＯＨが化学式３（化３） However, A is a divalent group which is a water-soluble polyoxyalkylene polyol (compound A) having a hydroxyl group at both ends of HO-A-OH and having a number average molecular weight of 400 to 100,000. The polyoxyalkylene polyol is a polymer of ethylene oxide, and B is selected from the group consisting of polyisocyanates having 3 to 18 OCN-B-NCO in which the total number of carbon atoms (including carbon of the NCO group) is 3 to 18. It is a divalent group that is a polyisocyanate compound (compound B), and D is HO-D-OH.
（ただし、Ｒ1は炭素数が１〜２０の炭化水素基ないし窒素含有炭化水素基である。またＲ2およびＲ3は炭素数が４〜２１の炭化水素基である。また該炭化水素基Ｒ1、 Ｒ2およびＲ3中の水素の一部ないし全部はフッ素、塩素、臭素ないし沃素で置換されていてもよく、Ｒ2とＲ3は同じでも異なっていてもよい。またＹおよびＹ’は水素、メチル基ないしＣＨ２Ｃｌ基であり、 ＹとＹ’は同じでも異なっていてもよい。またＺおよびＺ’は酸素、硫黄ないしＣＨ２基であり、ＺとＺ’は同じでも異なっていてもよい。またｎはＺが酸素の場合は０〜１５の整数であり、Ｚが硫黄ないし ＣＨ２基の場合は０である。またｎ’はＺ’が酸素の場合は０〜１５の整数であり、Ｚ’が硫黄ないし ＣＨ２基の場合は０であり、ｎとｎ’は同じでも異なっていてもよい）で表わされる櫛形ジオール（化合物Ｄ）である２価基である。
(However, R1 is a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group. R2 and R3 are hydrocarbon groups having 4 to 21 carbon atoms. The hydrocarbon groups R1, R2 And some or all of the hydrogen atoms in R3 may be substituted with fluorine, chlorine, bromine or iodine, and R2 and R3 may be the same or different, and Y and Y 'may be hydrogen, a methyl group or CH2Cl. Y and Y ′ may be the same or different, Z and Z ′ may be oxygen, sulfur or CH 2 groups, Z and Z ′ may be the same or different, and n is the same as Z In the case of oxygen, it is an integer from 0 to 15, and in the case where Z is sulfur or CH 2, it is 0. Also, when Z ′ is oxygen, n ′ is an integer from 0 to 15 and Z ′ is sulfur or CH 2. In the case of a group, it is 0, and n and n ′ may be the same or different Is a divalent group which is in comb diol represented (Compound D).
また本発明は、繰り返し単位（１）のモル比率が０．５以上０．９９以下であり、繰り返し単位（２）のモル比率が０．０１以上０．５以下であり、化合物Ａが数平均分子量３，０００〜２０，０００のポリエチレングリコールであり、化合物Ｂが全炭素数が（ＮＣＯ基の炭素を含めて）３〜１８の脂肪族ジイソシアナート類よりなる群から選ばれたジイソシアナート化合物であり、重量平均分子量が１万から１００万の範囲にある該水溶性ポリウレタンの製造方法に関する。 In the present invention, the molar ratio of the repeating unit (1) is from 0.5 to 0.99, the molar ratio of the repeating unit (2) is from 0.01 to 0.5, and the compound A has a number average. Diisocyanate selected from the group consisting of aliphatic diisocyanates having a molecular weight of 3,000 to 20,000 and compound B having 3 to 18 total carbon atoms (including carbon of NCO group) The present invention relates to a method for producing the water-soluble polyurethane, which is a compound and has a weight average molecular weight in the range of 10,000 to 1,000,000.
また本発明は、化合物Ｄが化学式４（化４） In the present invention, the compound D is represented by the chemical formula 4
（ただし、Ｒ1'は炭素数が４〜１８の鎖状アルキル基であり、Ｒ2'およびＲ3'は炭素数が４〜１８のアルキル基ないしアリール基であり、Ｒ1'、Ｒ2'およびＲ3'の炭素数の合計が１２〜４０であり、Ｒ2'とＲ3'は同じ）で表わされる櫛形ジオールである該水溶性ポリウレタンの製造方法に関する。
(However, R1 'is a chain alkyl group having 4 to 18 carbon atoms, R2' and R3 'are alkyl or aryl groups having 4 to 18 carbon atoms, and R1', R2 'and R3' The present invention relates to a method for producing the water-soluble polyurethane, which is a comb-shaped diol having a total number of carbon atoms of 12 to 40 and R2 ′ and R3 ′ being the same.
また本発明は、化合物Ｂがヘキサメチレンジイソシアナート、イソホロンジイソシアナート、水素化トリレンジイソシアナートまたはノルボルネンジイソシアナートである該水溶性ポリウレタンの製造方法に関する。 The present invention also relates to a process for producing the water-soluble polyurethane, wherein the compound B is hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate or norbornene diisocyanate.
本発明により、モルタルの保形性と成形品の強度に優れた新しい櫛形疎水基を有する水溶性ポリウレタンを塊砕することなく、粉末体を得ることができる。 According to the present invention, it is possible to obtain a powder body without crushing a water-soluble polyurethane having a new comb-shaped hydrophobic group excellent in mortar shape retention and strength of a molded product.
本発明により得られる高分子は、水溶性ポリオキシアルキレンと実質的に単分散の櫛形ジオールをポリイソシアナートで連結して得られる櫛形疎水基を有する高分子である。 The polymer obtained by the present invention is a polymer having a comb-shaped hydrophobic group obtained by linking a water-soluble polyoxyalkylene and a substantially monodispersed comb-shaped diol with a polyisocyanate.
化合物Ａ
本発明で用いられる水溶性ポリオキシアルキレンポリオール（化合物Ａ）は、少なくとも高分子鎖の両末端に水酸基を有するアルキレンオキサイド重合体である。
Compound A
The water-soluble polyoxyalkylene polyol (compound A) used in the present invention is an alkylene oxide polymer having hydroxyl groups at both ends of the polymer chain.
ただし水酸基を３個以上有するポリオキシアルキレンポリオールを用いると、製品の水への溶解性が低下しやすい。従って、高分子鎖の両末端に１級水酸基を有するポリアルキレングリコールを用いることがより好ましい。 However, when a polyoxyalkylene polyol having 3 or more hydroxyl groups is used, the solubility of the product in water tends to be lowered. Therefore, it is more preferable to use polyalkylene glycol having primary hydroxyl groups at both ends of the polymer chain.
単量体のアルキレンオキサイドとしてはエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、エピクロロヒドリンなどがあるが、水溶性を高めるためにはエチレンオキサイドの含有率が６０重量％以上あることがより好ましい。更に好ましくは、エチレンオキサイドの重合物（ポリエチレングリコール。以下ＰＥＧと略記する。）を用いることである。 Examples of the monomeric alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and epichlorohydrin. In order to improve water solubility, the ethylene oxide content is more preferably 60% by weight or more. More preferably, an ethylene oxide polymer (polyethylene glycol, hereinafter abbreviated as PEG) is used.
該化合物Ａの分子量は数平均分子量で４００〜１００，０００のものが好ましい。より好ましくは１，５００〜５０，０００、更に好ましくは３，０００〜２０，０００である。分子量が４００未満では十分な水溶液粘度を示す製品が得られず、増粘剤に用いることができない。また分子量が１００，０００より大きくなると反応速度が低下し、やはり十分な水溶液粘度を示す製品が得られない。分子量が３，０００〜２０，０００の範囲で、十分な水溶液粘度を示す製品が最も得られ易い。数平均分子量はゲル浸透クロマトグラフィー（ＧＰＣ）にて測定し、カラムにはショウデックズＫＤ−８０６Ｍを２本用いた。 The molecular weight of the compound A is preferably 400 to 100,000 in terms of number average molecular weight. More preferably, it is 1,500-50,000, More preferably, it is 3,000-20,000. If the molecular weight is less than 400, a product exhibiting sufficient aqueous solution viscosity cannot be obtained, and it cannot be used as a thickener. On the other hand, when the molecular weight is greater than 100,000, the reaction rate decreases and a product exhibiting sufficient aqueous solution viscosity cannot be obtained. A product exhibiting a sufficient aqueous solution viscosity with a molecular weight in the range of 3,000 to 20,000 is most easily obtained. The number average molecular weight was measured by gel permeation chromatography (GPC), and two Shodex KD-806M were used for the column.
化合物Ｂ
本発明で用いられるポリイソシアナート化合物（化合物Ｂ）は、鎖状脂肪族ポリイソシアナート類、環状脂肪族ポリイソシアナート類および芳香族ポリイソシアナートよりなる群から選ばれた全炭素数が（ＮＣＯ基の炭素を含めて）３〜１８のポリイソシアナート化合物である。ポリイソシアナート類の全炭素数が１８より大きいと、高分子の溶解性が低下し易い。
Compound B
The polyisocyanate compound (compound B) used in the present invention has a total carbon number selected from the group consisting of chain aliphatic polyisocyanates, cycloaliphatic polyisocyanates and aromatic polyisocyanates (NCO 3-18 polyisocyanate compounds (including the group carbon). If the total number of carbon atoms of the polyisocyanates is greater than 18, the solubility of the polymer tends to be lowered.
ただし分子内にＮＣＯ基３個以上有するポリイソシアナート類を用いると、製品の水への溶解性が低下しやすい。従って、分子内にＮＣＯ基を２個有するジイソシアナート類を用いることがより好ましい。 However, when polyisocyanates having 3 or more NCO groups in the molecule are used, the solubility of the product in water tends to be lowered. Therefore, it is more preferable to use diisocyanates having two NCO groups in the molecule.
また、芳香族ジイソシアナート類を用いて製造した高分子は、強塩基性であるモルタル中で経時変化をきたし、混練後時間とともに助剤としての効果が低下することがある。モルタルはｐＨが約１４の強アルカリなので、アルカリによる加水分解を受け易い芳香族ジイソシアナート類とポリアルキレングリコール間の結合が、切断されるためと考えられる。 In addition, polymers produced using aromatic diisocyanates change over time in mortar which is strongly basic, and the effect as an auxiliary agent may decrease with time after kneading. Since mortar is a strong alkali having a pH of about 14, it is considered that the bond between the aromatic diisocyanate and polyalkylene glycol that are susceptible to hydrolysis by alkali is broken.
従って、全炭素数が３〜１８の鎖状および環状脂肪族ジイソシアナート類を用いることがより好ましい。更に好ましくはヘキサメチレンジイソシアナート（通称ＨＤＩと略す）、イソホロンジイソシアナート（通称ＩＰＤＩと略す）、水素化キシリレンジイソシアナート（通称ＨＸＤＩと略す）またはノルボルナンジイソシアナートメチル（通称ＮＢＤＩと略す）を用いることである。特に好ましくは、ＨＤＩを用いることである。 Therefore, it is more preferable to use chain and cyclic aliphatic diisocyanates having 3 to 18 carbon atoms. More preferably, hexamethylene diisocyanate (commonly abbreviated as HDI), isophorone diisocyanate (commonly abbreviated as IPDI), hydrogenated xylylene diisocyanate (commonly abbreviated as HXDI) or norbornane diisocyanate methyl (commonly abbreviated as NBDI). Is to use. Particular preference is given to using HDI.
鎖状脂肪族ジイソシアナート類は、ＮＣＯ基の間を直鎖もしくは分岐鎖のアルキレン基で繋いだ構造をもつジイソシアナート化合物であり、具体例としては、メチレンジイソシアナート、エチレンジイソシアナート、トリメチレンジイソシアナート、１−メチルエチレンジイソシアナート、テトラメチレンジイソシアナート、ペンタメチレンジイソシアナート、２−メチルブタン−１，４−ジイソシアナート、ヘキサメチレンジイソシアナート（ＨＤＩ）、ヘプタメチレンジイソシアナート、２，２’−ジメチルペンタン−１，５−ジイソシアナート、リジンジイソシアナートメチルエステル（ＬＤＩ）、オクタメチレンジイソシアナート、２，５−ジメチルヘキサン−１，６−ジイソシアナート、２，２，４−トリメチルペンタン−１，５−ジイソシアナート、ノナメチルジイソシアナート、２，４，４−トリメチルヘキサン−１，６−ジイソシアナート、デカメチレンジイソシアナート、ウンデカメチレンジイソシアナート、ドデカメチレンジイソシアナート、トリデカメチレンジイソシアナート、テトラデカメチレンジイソシアナート、ペンタデカメチレンジイソシアナート、ヘキサデカメチレンジイソシアナート、トリメチルヘキサメチレンジイソシアナートなどが挙げられる。 A chain aliphatic diisocyanate is a diisocyanate compound having a structure in which NCO groups are connected by a linear or branched alkylene group. Specific examples thereof include methylene diisocyanate and ethylene diisocyanate. , Trimethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene Diisocyanate, 2,2′-dimethylpentane-1,5-diisocyanate, lysine diisocyanate methyl ester (LDI), octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate 2,2,4-trimethylpentane-1,5 Diisocyanate, nonamethyl diisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, decamethylene diisocyanate, undecamethylene diisocyanate, dodecamethylene diisocyanate, tridecamethylene diisocyanate Tetradecamethylene diisocyanate, pentadecamethylene diisocyanate, hexadecamethylene diisocyanate, trimethylhexamethylene diisocyanate and the like.
環状脂肪族ジイソシアナート類は、ＮＣＯ基の間を繋ぐアルキレン基が環状構造をもつジイソシアナート化合物であり、具体例としては、シクロヘキサン−１，２−ジイソシアナート、シクロヘキサン−１，３−ジイソシアナート、シクロヘキサン−１，４−ジイソシアナート、１−メチルシクロヘキサン−２，４−ジイソシアナート、１−メチルシクロヘキサン−２，６−ジイソシアナート、１−エチルシクロヘキサン−２，４−ジイソシアナート、４，５−ジメチルシクロヘキサン−１，３−ジイソシアナート、１，２−ジメチルシクロヘキサン−ω，ω’−ジイソシアナート、１，４−ジメチルシクロヘキサン−ω，ω’−ジイソシアナート、イソホロンジイソシアナート（ＩＰＤＩ）、ジシクロヘキシルメタン−４，４’−ジイソシアナート、ジシクロヘキシルメチルメタン−４，４’−ジイソシアナート、ジシクロヘキシルジメチルメタン−４，４’−ジイソシアナート、２，２’−ジメチルジシクロヘキシルメタン−４，４’−ジイソシアナート、３，３’−ジメチルジシクロヘキシルメタン−４，４’−ジイソシアナート、４，４’−メチレン−ビス（イソシアナトシクロヘキサン）、イソプロピリデンビス（４−シクロヘキシルイソシアナート）（ＩＰＣＩ）、１，３−ビス（イソシアナトメチル）シクロヘキサン、水素化トリレンジイソシアナート（ＨＴＤＩ）、水素化４，４’−ジフェニルメタンジイソシアナート（ＨＭＤＩ）、水素化キシリレンジイソシアナート（ＨＸＤＩ）、ノルボルナンジイソシアナートメチル（ＮＢＤＩ）などが挙げられる。 Cycloaliphatic diisocyanates are diisocyanate compounds in which the alkylene group connecting the NCO groups has a cyclic structure. Specific examples include cyclohexane-1,2-diisocyanate, cyclohexane-1,3- Diisocyanate, cyclohexane-1,4-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1-methylcyclohexane-2,6-diisocyanate, 1-ethylcyclohexane-2,4-di Isocyanate, 4,5-dimethylcyclohexane-1,3-diisocyanate, 1,2-dimethylcyclohexane-ω, ω′-diisocyanate, 1,4-dimethylcyclohexane-ω, ω′-diisocyanate, Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate Dicyclohexylmethylmethane-4,4′-diisocyanate, dicyclohexyldimethylmethane-4,4′-diisocyanate, 2,2′-dimethyldicyclohexylmethane-4,4′-diisocyanate, 3,3 '-Dimethyldicyclohexylmethane-4,4'-diisocyanate, 4,4'-methylene-bis (isocyanatocyclohexane), isopropylidenebis (4-cyclohexylisocyanate) (IPCI), 1,3-bis (isocyanate) Natomethyl) cyclohexane, hydrogenated tolylene diisocyanate (HTDI), hydrogenated 4,4′-diphenylmethane diisocyanate (HMDI), hydrogenated xylylene diisocyanate (HXDI), norbornane diisocyanate methyl (NBDI), etc. Can be mentioned.
芳香族ジイソシアナート類は、ＮＣＯ基の間をフェニレン基、アルキル置換フェニレン基およびアラルキレン基などの芳香族基ないし芳香族基を含有する炭化水素基で繋いだジイソシアナート化合物であり、具体例としては、１，３−および１，４−フェニレンジイソシアナート、１−メチル−２，４−フェニレンジイソシアナート（２，４−ＴＤＩ）、１−メチル−２，６−フェニレンジイソシアナート（２，６−ＴＤＩ）、１−メチル−２，５−フェニレンジイソシアナート、１−メチル−３，５−フェニレンジイソシアナート、１−エチル−２，４−フェニレンジイソシアナート、１−イソプロピル−２，４−フェニレンジイソシアナート、１，３−ジメチル−２，４−フェニレンジイソシアナート、１，３−ジメチル−４，６−フェニレンジイソシアナート、１，４−ジメチル−２，５−フェニレンジイソシアナート、ｍ−キシレンジイソシアナート、ジエチルベンゼン
ジイソシアナート、ジイソプロピルベンゼンジイソシアナート、１−メチル−３，５−ジエチルベンゼン−２，４−ジイソシアナート、３−メチル−１，５−ジエチルベンゼン−２，４−ジイソシアナート、１，３，５−トリエチルベンゼン−２，４−ジイソシアナート、ナフタリン−１，４−ジイソシアナート、ナフタリン−１，５−ジイソシアナート、１−メチルナフタリン−１，５−ジイソシアナート、ナフタリン−２，６−ジイソシアナート、ナフタリン−２，７−ジイソシアナート、１，１−ジナフチル−２，２’−ジイソシアナート、ビフェニル−２，４’−ジイソシアナート、ビフェニル−４，４’−ジイソシアナート、１，３−ビス（１−イソシアナト−１−メチルエチル）ベンゼン、３，３’−ジメチルビフェニル−４，４’−ジイソシアナート、ジフェニルメタン−４，４’−ジイソシアナート（ＭＤＩ）、ジフェニルメタン−２，２’−ジイソシアナート、
ジフェニルメタン−２，４’−ジイソシアナート、キシリレンジイソシアナート（ＸＤＩ）などが挙げられる。
Aromatic diisocyanates are diisocyanate compounds in which NCO groups are connected by aromatic groups such as phenylene groups, alkyl-substituted phenylene groups and aralkylene groups or hydrocarbon groups containing aromatic groups. 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate (2,4-TDI), 1-methyl-2,6-phenylene diisocyanate ( 2,6-TDI), 1-methyl-2,5-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl- 2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phen Range isocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, m-xylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethylbenzene-2,4 -Diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, Naphthalene-1,5-diisocyanate, 1-methylnaphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2 , 2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4 , 4'-diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-di Isocyanate (MDI), diphenylmethane-2,2′-diisocyanate,
Examples include diphenylmethane-2,4′-diisocyanate and xylylene diisocyanate (XDI).
その他のポリイソシアナートとしては１，６，１１−ウンデカトリイソシアナート、１，８−ジイソシアナート−４−イソシアナートメチルオクタン、１，３，６−ヘキサメチレントリイソシアナートなどが挙げられる。 Examples of other polyisocyanates include 1,6,11-undecatriisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, and the like.
化合物Ｄ
本発明で用いられる櫛形ジオール（化合物Ｄ）は、化学式３（化５）
Compound D
The comb-shaped diol (compound D) used in the present invention has the chemical formula 3
で表わされる、２級水酸基を分子内に２個有し、疎水鎖を分子内に３本有するジオール類である。
These are diols having two secondary hydroxyl groups in the molecule and three hydrophobic chains in the molecule.
ただし、Ｒ1は炭素数が１〜２０のアルキル基、アルケニル基、アラルキル基またはアリール基等の炭化水素基、ないしジアルキルアミノアルキル基等の窒素含有炭化水素基である。またＲ2およびＲ3は炭素数が４〜２１のアルキル基、アルケニル基、アラ ルキル基またはアリール基等の炭化水素基である。また炭化水素基Ｒ1、 Ｒ2およびＲ3中の水素の一部ないし全部はフッ素、塩素、臭素ないし沃素などのハロゲン原子で置換されていてもよい。Ｒ2とＲ3は同じでも異なっていてもよいが、同じであることがより好ましい。またＹおよびＹ’は水素、メチル基ないしＣＨ２Ｃｌ基であり、 ＹとＹ’は同じでも異なっていてもよいが、同じであることがより好ましい。またＺおよびＺ’は酸素、硫黄ないしＣＨ２基であり、ＺとＺ’は同じでも異なっていてもよいが、同じであることがより好ましい。更に好ましくはＺおよびＺ’がともに酸素であることである。またｎはＺが酸素の場合は０〜１５の整数であり、Ｚが硫黄ないし ＣＨ２基の場合は０である。またｎ’はＺ’が酸素の場合は０〜１５の整数であり、Ｚ’が硫黄ないし ＣＨ２基の場合は０であり、ｎとｎ’は同じでも異なっていてもよいが、同じであることがより好ましい。 R1 is a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aralkyl group or an aryl group, or a nitrogen-containing hydrocarbon group such as a dialkylaminoalkyl group. R2 and R3 are hydrocarbon groups such as alkyl groups, alkenyl groups, aralkyl groups or aryl groups having 4 to 21 carbon atoms. Some or all of hydrogen in the hydrocarbon groups R1, R2 and R3 may be substituted with halogen atoms such as fluorine, chlorine, bromine or iodine. R2 and R3 may be the same or different, but are preferably the same. Y and Y 'are hydrogen, a methyl group or a CH2Cl group, and Y and Y' may be the same or different, but are preferably the same. Z and Z 'are oxygen, sulfur or CH2 groups, and Z and Z' may be the same or different, but are preferably the same. More preferably, both Z and Z 'are oxygen. N is an integer of 0 to 15 when Z is oxygen, and 0 when Z is sulfur or a CH2 group. N ′ is an integer of 0 to 15 when Z ′ is oxygen, and 0 when Z ′ is sulfur or CH 2 group, and n and n ′ may be the same or different but are the same. It is more preferable.
以下に櫛形ジオールの製造方法を説明するが、本発明に用いる櫛形ジオールの合成方法はこの例に限定されるものではない。 Although the manufacturing method of a comb-shaped diol is demonstrated below, the synthesis method of the comb-shaped diol used for this invention is not limited to this example.
櫛形ジオールの製造
攪拌装置、原料導入機構、温度制御機構を有する反応容器に、原料のアミン類とオキシラン化合物類を仕込み、所定の反応温度において撹拌しながら反応させる。反応は無溶媒で行うことができるが、ＤＭＦなどの一般的な溶媒を用いてもよい。原料の導入は、アミン類とオキシラン化合物類を一括して仕込んでもよいし、どちらか一方を反応容器に仕込み、他方を連続的ないし段階的に導入してもよい。反応温度は室温〜１６０℃程度、より好ましくは６０℃〜１２０℃程度が適当である。反応時間は、反応温度等にも依るが、０．５〜１０時間程度である。反応終了後のジオールは、ＧＰＣにより分散度を求めることができる。また常法によりＯＨ価を求めることができる。
A raw material amine and an oxirane compound are charged into a reaction vessel having a comb-shaped diol production stirring apparatus, a raw material introduction mechanism, and a temperature control mechanism, and reacted at a predetermined reaction temperature with stirring. The reaction can be carried out without solvent, but a general solvent such as DMF may be used. For the introduction of the raw materials, the amines and oxirane compounds may be charged all together, or one of them may be charged into the reaction vessel and the other may be introduced continuously or stepwise. The reaction temperature is suitably about room temperature to 160 ° C, more preferably about 60 ° C to 120 ° C. The reaction time is about 0.5 to 10 hours although it depends on the reaction temperature and the like. The degree of dispersion of the diol after completion of the reaction can be determined by GPC. Moreover, OH value can be calculated | required by a conventional method.
プレポリマーの製造
ジイソシアナート化合物と櫛形ジオール化合物の付加反応により、プレポリマーを得る。攪拌装置、原料導入機構、温度制御機構を有する反応容器内を不活性ガスで置換する。ジイソシアナート化合物と櫛形ジオール化合物を室温にて、ジイソシアナート化合物が櫛形ジオールよりも反応等量よりも過剰となるように仕込み、所定の反応温度まで昇温し、櫛形ジオールがほぼジイソシアナート化合物と反応するまで保持する。プレポリマー合成反応に用いるジイソシアナート化合物の量は、櫛形ジオール１モルに対して、ジイソシアナート化合物のモル数（ＮＣＯ／ＯＨ）が１〜１００モル、より好ましくは２〜５０モル、更に好ましくは３〜１０である。 反応温度はジイソシアナート化合物種、櫛形ジオール種によっても異なるが、２０〜１８０℃が適当である。より好ましくは４０〜１２０℃、さらに好ましくは６０〜１００℃の範囲である。反応時間は、反応温度などに
より異なり特に限定するものではないが、１分〜１００時間程度である。
Preparation of prepolymer A prepolymer is obtained by addition reaction of a diisocyanate compound and a comb diol compound. The inside of the reaction vessel having a stirrer, a raw material introduction mechanism, and a temperature control mechanism is replaced with an inert gas. The diisocyanate compound and the comb diol compound are charged at room temperature so that the diisocyanate compound is in excess of the reaction equivalent than the comb diol, the temperature is raised to a predetermined reaction temperature, and the comb diol is almost diisocyanate. Hold until reacted with compound. The amount of the diisocyanate compound used in the prepolymer synthesis reaction is 1 to 100 moles, more preferably 2 to 50 moles, and still more preferably 1 mole of the diisocyanate compound (NCO / OH) with respect to 1 mole of the comb diol. Is 3-10. The reaction temperature varies depending on the diisocyanate compound species and the comb diol species, but 20 to 180 ° C is suitable. More preferably, it is 40-120 degreeC, More preferably, it is the range of 60-100 degreeC. The reaction time varies depending on the reaction temperature and is not particularly limited, but is about 1 minute to 100 hours.
水溶性ポリウレタンの製造
櫛形疎水基を有する水溶性ポリウレタンは、化学式１０（化６）
Production of water-soluble polyurethane Water-soluble polyurethane having a comb-shaped hydrophobic group is represented by the chemical formula 10
に表すように、ポリアルキレングリコール（化合物Ａ）および櫛形ジオール（化合物Ｄ）の２個の水酸基とジイソシアナート化合物（化合物Ｂ）の２個のＮＣＯ基の反応により合成される。繰り返し単位（１）のモル比率が（１−ｘ）でかつ繰り返し単位（２）のモル比率がｘである水溶性ポリウレタンは、化合物Ａと化合物Ｄのモル比率が（１−ｘ）：ｘの比率で反応させることにより得られる。
As shown in FIG. 4, the compound is synthesized by the reaction of two hydroxyl groups of polyalkylene glycol (compound A) and comb-shaped diol (compound D) and two NCO groups of diisocyanate compound (compound B). The water-soluble polyurethane in which the molar ratio of the repeating unit (1) is (1-x) and the molar ratio of the repeating unit (2) is x is such that the molar ratio of the compound A and the compound D is (1-x): x. It is obtained by reacting at a ratio.
以下に水溶性ポリウレタンの製造方法を例を挙げて説明するが、勿論本発明は以下の製造方法に限定されるものではない。 Hereinafter, the production method of the water-soluble polyurethane will be described by way of example, but the present invention is of course not limited to the following production method.
攪拌装置、原料導入機構、温度制御機構を有する反応容器内を不活性ガスで置換する。ポリアルキレングリコールを、反応容器へ仕込む。ポリアルキレングリコールは分子量によって融点が異なるため、使用するポリアルキレングリコールの融点以上となって、容器内を攪拌しつつ予め合成したプレポリマーとジイソシアナート化合物を反応容器へ導入する。導入方法は特に限定するものではない。
連続的に導入しても断続的に導入してもよい。またジイソシアナート化合物と櫛形ジオールは、同時に導入しても、ジイソシアナート化合物の導入後に櫛形ジオールを導入しても、櫛形ジオールの導入後にジイソシアナート化合物を導入してもよい。その後、水溶性ポリウレタンの不溶性溶媒を仕込む。
The inside of the reaction vessel having a stirrer, a raw material introduction mechanism, and a temperature control mechanism is replaced with an inert gas. A polyalkylene glycol is charged into a reaction vessel. Since the polyalkylene glycol has a melting point that varies depending on the molecular weight, the prepolymer and the diisocyanate compound synthesized in advance are introduced into the reaction vessel while stirring in the vessel, with the melting point being higher than that of the polyalkylene glycol to be used. The introduction method is not particularly limited.
It may be introduced continuously or intermittently. In addition, the diisocyanate compound and the comb diol may be introduced simultaneously, the comb diol may be introduced after the diisocyanate compound is introduced, or the diisocyanate compound may be introduced after the comb diol is introduced. Thereafter, an insoluble solvent of water-soluble polyurethane is charged.
水溶性ポリウレタンの不溶性溶媒としては、例えばヘキサン、ヘプタン、オクタン、ペンタン、シクロヘキサンなどの脂肪族炭化水素を主成分とし、０〜８０％の重量割合範囲で、一種あるいは二種以上のエステル系溶媒、ケトン系溶媒、芳香族溶媒、分散剤を含むものが使用される。エステル系溶媒としては、酢酸メチル、酢酸エチル、酢酸−ｎ−ブチル、酢酸イソブチル、酢酸アミルなどの各種エステル類や、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ−ｎ−ブチルエーテルアセテート、エチルエトキシプロピオネト等の各種アルコキシ基を有するエステル類が挙げられる。ケトン系溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルイソブチルケトン、メチルアミルケトン
、シクロヘキサノン等が、芳香族溶媒としては、トルエン、キシレン、エチルベンゼン等が挙げられる。
As an insoluble solvent for water-soluble polyurethane, for example, a main component is an aliphatic hydrocarbon such as hexane, heptane, octane, pentane, cyclohexane and the like, in a weight ratio range of 0 to 80%, one or more ester solvents, What contains a ketone solvent, an aromatic solvent, and a dispersing agent is used. As ester solvents, various esters such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether Examples include esters having various alkoxy groups such as acetate and ethylethoxypropionate. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone. Examples of the aromatic solvent include toluene, xylene, and ethylbenzene.
本発明で用いる分散剤とは、上記した非水溶媒に溶解し、非水溶媒中で水溶性の原料およびポリウレタン重合体を安定して分散させる効果を有するものである。本発明では特に、（１）アルケニル無水コハク酸とポリオールあるいはポリエステルポリオールとを脱水縮合させた樹脂、（２）ジカルボン酸とペンタエリスリトールとを脱水縮合させたポリエステルの残OH基の一部に脂肪酸を脱水縮合させたアルキッド樹脂、（３）不飽和結合含有ジカルボン酸とポリオールあるいはポリエステルポリオールとの脱水縮合で得られるポリオールにエチレン性不飽和単量体をグラフト重合させた後、OH基をマスキングした樹脂、（４）不飽和結合含有ジカルボン酸とポリオールあるいはポリエステルポリオールとの脱水縮合で得られるポリオールのOH基をマスキングした後、エチレン性不飽和単量体をグラフト重合させた樹脂を用いる。
本発明で用いるアルケニル無水コハク酸とは、例えばα−オレフィンを無水マレイン酸上に間接的に置換して付加するいわゆるエン−合成によって得られる既知化合物である。
またポリオールあるいはポリエステルポリオールとしては、分子内に少なくとも２個のOH基を有する化合物であり、ポリアルキレンエーテルグリコール、ジオールとジカルボン酸を重合させて得られるポリエステル、及びこれらの混合物が用いられる。
またアルキッド樹脂で用いられるジカルボン酸としては、イソフタル酸、テレフタル酸等の芳香族二塩基酸、アジピン酸、セバシン酸等の脂肪族二塩基酸が用いられる。また不飽和結合含有ジカルボン酸とはマレイン酸、イタコン酸などがあり、さらにその無水物でも使用できる。
またOH基をマスキングする試薬としてはOH基と反応する官能基を分子内に１つ有し、他の末端基が非水分散重合反応系で不活性な官能基を有する化合物であれば特に限定されないが、例えばイソシアン酸エチル、イソシアン酸ブチル、イソシアン酸ヘキシル等のモノアルキルイシアネート類が挙げられる。
The dispersant used in the present invention has an effect of being dissolved in the above-described non-aqueous solvent and stably dispersing the water-soluble raw material and the polyurethane polymer in the non-aqueous solvent. In the present invention, in particular, (1) a resin obtained by dehydration condensation of an alkenyl succinic anhydride and a polyol or polyester polyol, and (2) a fatty acid is partially added to a residual OH group of a polyester obtained by dehydration condensation of a dicarboxylic acid and pentaerythritol. Dehydration-condensed alkyd resin, (3) A resin obtained by graft polymerization of an ethylenically unsaturated monomer to a polyol obtained by dehydration condensation of an unsaturated bond-containing dicarboxylic acid and a polyol or polyester polyol, and then masking the OH group (4) A resin obtained by masking the OH group of a polyol obtained by dehydration condensation of an unsaturated bond-containing dicarboxylic acid and a polyol or polyester polyol and then graft-polymerizing an ethylenically unsaturated monomer is used.
The alkenyl succinic anhydride used in the present invention is a known compound obtained by, for example, so-called ene synthesis in which an α-olefin is indirectly substituted on maleic anhydride for addition.
The polyol or polyester polyol is a compound having at least two OH groups in the molecule, and polyalkylene ether glycol, polyester obtained by polymerizing diol and dicarboxylic acid, and mixtures thereof are used.
As the dicarboxylic acid used in the alkyd resin, aromatic dibasic acids such as isophthalic acid and terephthalic acid, and aliphatic dibasic acids such as adipic acid and sebacic acid are used. Examples of the unsaturated bond-containing dicarboxylic acid include maleic acid and itaconic acid, and anhydrides thereof can also be used.
The reagent for masking the OH group is particularly limited as long as it has one functional group that reacts with the OH group in the molecule and the other terminal group has a functional group that is inactive in the non-aqueous dispersion polymerization reaction system. Although not mentioned, for example, monoalkyl isocyanates such as ethyl isocyanate, butyl isocyanate, hexyl isocyanate and the like can be mentioned.
反応温度を制御しつつ、触媒を加える。触媒は必ずしも不溶性溶媒添加後である必要はなく、ポリアルキレングリコールにジイソシアナート化合物やプレポリマーを加えた後に触媒を加え、反応を開始することも可能である。または、ジイソシアナート化合物やプレポリマーに予め触媒を添加しておき、これらをポリアルキレングリコールに加え反応させることも可能である。 The catalyst is added while controlling the reaction temperature. The catalyst is not necessarily required after the addition of the insoluble solvent, and the reaction can be started by adding the catalyst after adding the diisocyanate compound or prepolymer to the polyalkylene glycol. Alternatively, it is also possible to add a catalyst in advance to the diisocyanate compound or prepolymer, and add these to the polyalkylene glycol for reaction.
所定の反応時間後に生成物を反応容器から取り出し、固液分離後乾燥し製品とする。 After a predetermined reaction time, the product is taken out from the reaction vessel, separated into solid and liquid and dried to obtain a product.
反応に用いられる触媒は特に限定するものではなく、有機金属化合物、金属塩、３級アミン、その他の塩基触媒や酸触媒などの、一般にイソシアナート類とポリオール類の反応に用いられる公知の触媒を用いることができる。例を挙げれば、ジブチル錫ジラウレート（以下ＤＢＴＤＬと略す）、ジブチル錫ジアセテート、ジブチル錫ジ（ドデシルチオラート）、ジブチル錫ジ（ドデシルチオラート）、ジメチル錫ジラウレート、第一錫オクタノエート、１，１，３，３，−テトラブチルー１，３−ジラウリルオキシカルボニルージスタノキサン、ビスマストリス（２−エチルヘキサノエート）、フェニル水銀アセテート、亜鉛オクトエート、鉛オクトエート、亜鉛ナフテナート、鉛ナフテナート、トリエチルアミン（ＴＥＡ）、テトラメチルブタンジアミン（ＴＭＢＤＡ）、Ｎ−エチルモルホリン（
ＮＥＭ）、１，４−ジアザ［２．２．２］ビシクロオクタン（ＤＡＢＣＯ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン（ＤＢＵ）、Ｎ，Ｎ‘−ジメチル−１，４−ジアザシクロヘキサン（ＤＭＰ）などがある。なかでも錫、ビスマスを含む触媒が高活性のためより好ましい。
The catalyst used for the reaction is not particularly limited, and known catalysts generally used for the reaction of isocyanates and polyols such as organometallic compounds, metal salts, tertiary amines, other basic catalysts and acid catalysts are used. Can be used. Examples include dibutyltin dilaurate (hereinafter abbreviated as DBTDL), dibutyltin diacetate, dibutyltin di (dodecylthiolate), dibutyltin di (dodecylthiolate), dimethyltin dilaurate, stannous octanoate, 1,1,3 , 3, -tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, bismuth tris (2-ethylhexanoate), phenylmercuric acetate, zinc octoate, lead octoate, zinc naphthenate, lead naphthenate, triethylamine (TEA), Tetramethylbutanediamine (TMBDA), N-ethylmorpholine (
NEM), 1,4-diaza [2.2.2] bicyclooctane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), N, N′-dimethyl-1, 4-diazacyclohexane (DMP) and the like. Of these, a catalyst containing tin and bismuth is more preferable because of its high activity.
反応に用いる触媒の量は、反応温度や触媒の種類によっても異なり特に限定するものではないが、ポリアルキレングリコールの１モル当たり０．０００１〜０．１モル、より好ましくは０．００１〜０．１モル程度で十分である。 The amount of the catalyst used in the reaction varies depending on the reaction temperature and the type of the catalyst and is not particularly limited, but is 0.0001 to 0.1 mol, more preferably 0.001 to 0.1 mol per mol of the polyalkylene glycol. About 1 mole is sufficient.
ジイソシアナート化合物の量は、プレポリマー合成時とポリウレタン重合時の合計が、ポリアルキレングリコールと櫛形ジオールの各々のモル数の合計１モルに対して、ジイソシアナート化合物のモル数（ＮＣＯ／ＯＨ）が０．８〜１．３モル、より好ましくは０．９〜１．２モル、更に好ましくは１．０〜１．１である。ジイソシアネートのモル数とポリアルキレングリコールと櫛形ジオールのモル数の合計とがほぼ等量である条件で、最も分子量の大きな生成物が得られる。 The amount of the diisocyanate compound is based on the total number of moles of the diisocyanate compound (NCO / OH) with respect to the total of 1 mole of each of the polyalkylene glycol and the comb diol during the prepolymer synthesis and the polyurethane polymerization. ) Is 0.8 to 1.3 mol, more preferably 0.9 to 1.2 mol, and still more preferably 1.0 to 1.1. A product with the highest molecular weight can be obtained under the condition that the number of moles of diisocyanate and the total number of moles of polyalkylene glycol and comb diol are approximately equal.
ただし、ポリアルキレングリコールや櫛形ジオールに水分が含まれる場合には、上述のジイソシアナート化合物の量は、水分によりジイソシアナートが分解する分だけ余分に用いる必要がある。従って、十分に乾燥した原料を用いることがより好ましい。できれば原料に含まれる水分は、５，０００ｐｐｍ以下が好ましい。より好ましくは１，０００ｐｐｍ以下、更に好ましくは２００ｐｐｍ以下である。 However, when water is contained in the polyalkylene glycol or the comb diol, the amount of the above-mentioned diisocyanate compound needs to be used in excess as much as the diisocyanate is decomposed by water. Therefore, it is more preferable to use a sufficiently dried raw material. If possible, the moisture contained in the raw material is preferably 5,000 ppm or less. More preferably, it is 1,000 ppm or less, More preferably, it is 200 ppm or less.
反応に用いる櫛形ジオールの量は、ポリアルキレングリコールの分子量や櫛形ジオールの疎水基の炭素数によっても異なるが、櫛形ジオールのモル数がポリアルキレングリコールの１モル当たり０．００１〜１モル（ｘが０．００１〜０．５）が適当である。０．００１モル未満では、増粘効果が表われないことがある
。また１モルを超えて反応させることは、溶解性を低下させる場合があるので好ましくない。なお、（ ）内の数値は該化学式１０中のｘの値を表している。
The amount of the comb diol used in the reaction varies depending on the molecular weight of the polyalkylene glycol and the carbon number of the hydrophobic group of the comb diol, but the number of moles of the comb diol is 0.001 to 1 mole per mole of the polyalkylene glycol (x is 0.001 to 0.5) is suitable. If it is less than 0.001 mol, the thickening effect may not be exhibited. Moreover, it is not preferable to make it react exceeding 1 mol since solubility may be reduced. The numerical value in () represents the value of x in the chemical formula 10.
該ポリアルキレングリコールとして数平均分子量が３，０００〜２０，０００の範囲にあるポリエチレングリコールを用いた場合に、押出成形助剤として最も優れたポリウレタンが得られ易い。この場合に反応に用いる櫛形ジオールの量としては、ポリエチレングリコール１モル当たり０．０１〜１モル（ｘが０．０１〜０．５）がより好ましい。更に好ましくは０．０３〜０．６７モル（ｘが０．０３〜０．４）である。０．０１モル未満では、押出成形助剤としての効果が十分でないことがある。 When polyethylene glycol having a number average molecular weight in the range of 3,000 to 20,000 is used as the polyalkylene glycol, the most excellent polyurethane as an extrusion aid is easily obtained. In this case, the amount of the comb diol used for the reaction is more preferably 0.01 to 1 mol (x is 0.01 to 0.5) per mol of polyethylene glycol. More preferably, it is 0.03-0.67 mol (x is 0.03-0.4). If it is less than 0.01 mol, the effect as an extrusion aid may not be sufficient.
反応温度は用いる触媒の種類や量などによっても異なるが、５０〜１８０℃が適当である。より好ましくは６０〜１５０℃、さらに好ましくは８０〜１２０℃の範囲である。反応温度が５０℃未満では、反応速度が遅く経済的でない。また１８０℃を超えると、生成物が熱分解することがある。 The reaction temperature varies depending on the type and amount of the catalyst used, but 50 to 180 ° C. is appropriate. More preferably, it is 60-150 degreeC, More preferably, it is the range of 80-120 degreeC. If the reaction temperature is less than 50 ° C., the reaction rate is slow and not economical. Moreover, when it exceeds 180 degreeC, a product may thermally decompose.
反応時間は、用いる触媒の種類や量、反応温度などにより異なり特に限定するものではないが、１分〜１０時間程度で十分である。 The reaction time varies depending on the type and amount of the catalyst used, the reaction temperature, and the like, and is not particularly limited, but about 1 minute to 10 hours is sufficient.
反応圧力は、特に限定されない。常圧、減圧ないし加圧状態で、反応させることができる。より好ましくは、常圧ないし弱加圧状態で反応させる。 The reaction pressure is not particularly limited. The reaction can be carried out at normal pressure, reduced pressure or increased pressure. More preferably, the reaction is performed under normal pressure or weak pressure.
撹拌装置は、分散するに必要な攪拌条件が与えられるものが好ましい。そのための撹拌翼としては、一般的な撹拌翼（タービン、パドル、傾斜パドル、ファウドラー翼、イカリ翼など）でもよいし、ディスパー、ホモミキサー等を用いてもよい。これらの撹拌翼種と撹拌動力によって、製品粒子径を制御できる。製品粒子径は、製品の溶解速度を制御するために重要な因子であり、1〜５００μｍが好ましく、さらに好ましくは１０〜３００μｍである。 It is preferable that the stirring device is provided with stirring conditions necessary for dispersion. As a stirring blade for that purpose, a general stirring blade (such as a turbine, paddle, inclined paddle, fouler blade, or squid blade) may be used, or a disper, a homomixer, or the like may be used. The particle size of the product can be controlled by these stirring blade types and stirring power. The product particle size is an important factor for controlling the dissolution rate of the product, and is preferably 1 to 500 μm, more preferably 10 to 300 μm.
水溶性ポリウレタン
上記のようにして製造された水溶性ポリウレタンは、化学式１（化７）
Water-soluble polyurethane The water-soluble polyurethane produced as described above has the chemical formula 1
で表される繰り返し単位（２）からなる高分子であり、繰り返し単位（１）のモル比率が０．５以上０．９９９以下であり、繰り返し単位（２）のモル比率が０．００１以上０．５以下であり、重量平均分子量が１万から１，０００万の範囲にある水溶性ポリウレタンである。
The molar ratio of the repeating unit (1) is 0.5 or more and 0.999 or less, and the molar ratio of the repeating unit (2) is 0.001 or more and 0. It is a water-soluble polyurethane having a weight average molecular weight in the range of 10,000 to 10 million.
繰り返し単位（１）のモル比率が０．５以上０．９９９以下であり、繰り返し単位（２）のモル比率が０．００１以上０．５以下であると、水への溶解性がよく適度な増粘効果がある。 When the molar ratio of the repeating unit (1) is 0.5 or more and 0.999 or less, and the molar ratio of the repeating unit (2) is 0.001 or more and 0.5 or less, the solubility in water is good and appropriate. Has a thickening effect.
また、重量平均分子量が１万から１，０００万の範囲にあると、押し出し成形助剤として最も優れたポリウレタンが得られ易い。重量平均分子量はＧＰＣにて測定し、カラムにはショウデックズＫＤ−８０６Ｍを２本用いた。 Further, when the weight average molecular weight is in the range of 10,000 to 10 million, the most excellent polyurethane as an extrusion molding aid is easily obtained. The weight average molecular weight was measured by GPC, and two Shodex KD-806M were used for the column.
また、該水溶性ポリウレタンは、酸化防止剤、安定化剤、可塑剤、希釈剤、固結防止剤などを含んでいてもよい。これらの添加物は、重合中に添加しても良いし、重合後添加しても良い。 The water-soluble polyurethane may contain an antioxidant, a stabilizer, a plasticizer, a diluent, an anti-caking agent, and the like. These additives may be added during the polymerization or may be added after the polymerization.
以下に本発明の実施例を示すが、本発明はこれら実施例に限定されるものではない。 Examples of the present invention are shown below, but the present invention is not limited to these Examples.
［実施例１］
（１）プレポリマーの合成
５００ｍｌの４つ口セパラブルフラスコに、櫛形ジオール３０．５ｇ、ヘキサメチレンジイソシアナート（ＨＤＩ）６９．５ｇを仕込み（ＮＣＯ／ＯＨモル比＝６．９４）、反応器内にＮ2ガスを流しながら、オイルバスにて７０℃に昇温し８時間反応させる。得られたプレポリマーのＮＣＯ価は、２９．６％であった。櫛形ジオールは、２−エチルヘキシルアミン１モルに対して、２−エチルヘキシルグリシジルエーテルが２モルの比率で付加した化合物を用いた。
（２）水溶性ポリウレタン樹脂の非水分散重合
１０００ｍｌの４つ口セパラブルフラスコに、脱水したポリエチレングリコール（ＰＥＧ＃６０００、三洋化成工業品、数平均分子量８７６６）１００ｇ、２，６−ジーｔｅｒｔ−ブチルー４−メチルフェノール（ＢＨＴ、酸化防止剤）０．０５ｇを仕込み、反応器内にＮ2ガスを流しながら、攪拌機、温度計、冷却管を付ける。オイルバスにて７０℃に昇温し、ＰＥＧが溶解したら（１）で得たプレポリマーを３．２８ｇ、ＨＤＩを０．０６ｇ滴下ロートにて仕込み、攪拌混合する（ＰＥＧ：櫛形ジオール＝０．８５：０．１５、ＮＣＯ／ＯＨモル比＝１．０２）。イソオクタン／酢酸ブチル混合溶剤（酢酸ブチル３０重量％）３００ｇを反応器内にＮ2にて圧送した後、攪拌回転数を１０００ｒｐｍまで上げる。９０℃に昇温後、ジブチル錫ジラウレート（ＤＢＴＤＬ）触媒を０．０２ｇ添加し
、６時間反応させて、混合溶剤中に分散した粒子状の水溶性ポリウレタン樹脂を得た。水溶性ポリウレタン樹脂の主粒子径は約９０〜１２０μmで、重量平均分子量は約２９２，５００であった。
[Example 1]
(1) Synthesis of prepolymer A 500 ml four-necked separable flask was charged with 30.5 g of comb-shaped diol and 69.5 g of hexamethylene diisocyanate (HDI) (NCO / OH molar ratio = 6.94). While flowing N 2 gas inside, the temperature is raised to 70 ° C. in an oil bath and reacted for 8 hours. The NCO value of the obtained prepolymer was 29.6%. As the comb-shaped diol, a compound in which 2-ethylhexyl glycidyl ether was added at a ratio of 2 mol to 1 mol of 2-ethylhexylamine was used.
(2) Non-aqueous dispersion polymerization of water-soluble polyurethane resin In a 1000 ml four-necked separable flask, 100 g of dehydrated polyethylene glycol (PEG # 6000, Sanyo Chemical Industries, number average molecular weight 8766), 2,6-di-tert- 0.05 g of butyl-4-methylphenol (BHT, antioxidant) is charged, and a stirrer, a thermometer, and a cooling pipe are attached while flowing N 2 gas into the reactor. When the temperature is raised to 70 ° C. in an oil bath and PEG is dissolved, 3.28 g of the prepolymer obtained in (1) and 0.06 g of HDI are charged in a dropping funnel and mixed with stirring (PEG: comb diol = 0. 85: 0.15, NCO / OH molar ratio = 1.02). After 300 g of isooctane / butyl acetate mixed solvent (butyl acetate 30 wt%) is pumped into the reactor with N 2 , the stirring speed is increased to 1000 rpm. After raising the temperature to 90 ° C., 0.02 g of dibutyltin dilaurate (DBTDL) catalyst was added and reacted for 6 hours to obtain a particulate water-soluble polyurethane resin dispersed in a mixed solvent. The main particle size of the water-soluble polyurethane resin was about 90 to 120 μm, and the weight average molecular weight was about 292,500.
［実施例２］
溶剤として、酢酸ブチルの代わりにメチルイソブチルケトン（ＭＩＢＫ）を使用する以外は、実施例１と同様の操作を行う。
[Example 2]
The same operation as in Example 1 is performed except that methyl isobutyl ketone (MIBK) is used in place of butyl acetate as a solvent.
１０００ｍｌの４つ口セパラブルフラスコに、脱水したＰＥＧを１００ｇ、ＢＨＴを０．０５ｇを仕込み、反応器内にＮ2ガスを流しながら、攪拌機、温度計、冷却管を付ける。オイルバスにて７０℃に昇温し、ＰＥＧが溶解したら実施例１、（１）で得たプレポリマーを３．２８ｇ、ＨＤＩを０．０６ｇ滴下ロートにて仕込み、攪拌混合する（ＰＥＧ：櫛形ジオール＝０．８５：０．１５、ＮＣＯ／ＯＨモル比＝１．０２）。イソオクタン／ＭＩＢＫ混合溶剤（ＭＩＢＫ３０重量％）３００ｇを、反応器内にＮ2にて圧送した後、攪拌回転数を１０００ｒｐｍまで上げる。９０℃に昇温後、ＤＢＴＤＬを０．０２ｇ添加し、６時間反応させて、混合溶剤中に分散した粒子状の水溶性ポリウレタン樹脂を得た。水溶性ポリウレタン樹脂の主粒子径は約９０〜１４０μmで、重量平均分子量は約２９１，０００であった。 A 1000 ml four-necked separable flask is charged with 100 g of dehydrated PEG and 0.05 g of BHT, and a stirrer, a thermometer, and a condenser tube are attached while N 2 gas is allowed to flow into the reactor. When the temperature was raised to 70 ° C. in an oil bath and PEG was dissolved, 3.28 g of the prepolymer obtained in Example 1 and (1) and 0.06 g of HDI were charged in a dropping funnel and mixed by stirring (PEG: comb-shaped) Diol = 0.85: 0.15, NCO / OH molar ratio = 1.02). After 300 g of isooctane / MIBK mixed solvent (MIBK 30 wt%) is pumped into the reactor with N 2 , the stirring speed is increased to 1000 rpm. After raising the temperature to 90 ° C., 0.02 g of DBTDL was added and reacted for 6 hours to obtain a particulate water-soluble polyurethane resin dispersed in a mixed solvent. The main particle diameter of the water-soluble polyurethane resin was about 90 to 140 μm, and the weight average molecular weight was about 291,000.
［実施例３］
分散安定剤としてマリアリムＡＡＳ−０８５１（日本油脂製）を使用し、溶剤としてイソオクタンを単独で使用する以外は、実施例１と同様の操作を行う。
[Example 3]
The same operation as in Example 1 is performed except that Marialim AAS-0851 (manufactured by NOF Corporation) is used as a dispersion stabilizer and isooctane is used alone as a solvent.
１０００ｍｌの４つ口セパラブルフラスコに、脱水したＰＥＧを１００ｇ、ＢＨＴを０．０５ｇ仕込み、反応器内にＮ2ガスを流しながら、攪拌機、温度計、冷却管を付ける。オイルバスにて７０℃に昇温し、ＰＥＧが溶解したら実施例１、（１）で得たプレポリマーを３．２８ｇ、ＨＤＩを０．０６ｇ滴下ロートにて仕込み、攪拌混合する（ＰＥＧ：櫛形ジオール＝０．８５：０．１５、ＮＣＯ／ＯＨモル比＝１．０２）。マリアリム５ｇを溶解させたイソオクタン溶剤３００ｇを、反応器内にＮ2にて圧送した後、攪拌回転数を１０００ｒｐｍまで上げる。９０℃に昇温後、ＤＢＴＤＬを０．０２ｇ添加し、６時間反応させて、混合溶剤中に分散した粒子状の水溶性ポリウレタン樹脂を得た。水溶性ポリウレタン樹脂の主粒子径は約８０〜１１０μmで、重量平均分子量は約３０６，０００であった。 A 1000 ml four-necked separable flask is charged with 100 g of dehydrated PEG and 0.05 g of BHT, and a stirrer, a thermometer, and a condenser tube are attached while N 2 gas is allowed to flow into the reactor. When the temperature was raised to 70 ° C. in an oil bath and PEG was dissolved, 3.28 g of the prepolymer obtained in Example 1 and (1) and 0.06 g of HDI were charged in a dropping funnel and mixed by stirring (PEG: comb-shaped) Diol = 0.85: 0.15, NCO / OH molar ratio = 1.02). After 300 g of isooctane solvent in which 5 g of maria rim has been dissolved is pumped into the reactor with N 2 , the stirring speed is increased to 1000 rpm. After raising the temperature to 90 ° C., 0.02 g of DBTDL was added and reacted for 6 hours to obtain a particulate water-soluble polyurethane resin dispersed in a mixed solvent. The main particle diameter of the water-soluble polyurethane resin was about 80 to 110 μm, and the weight average molecular weight was about 306,000.
［実施例４］
・ 分散剤１の合成
東邦化学（株）製のポリブテニルコハク酸の酸価、ポリスチレン換算重量平均分子量を測定したところ、酸価は３８．０ｍｇＫＯＨ／ｇ、ポリスチレン換算重量平均分子量は３５００であった。これを２０．０ｇ、ポリエチレングリコール１０００（関東化学製）１０．０ｇを撹拌棒付の１００ｍｌの3つ口フラスコに入れ、窒素気流下、１８０℃で２０時間撹拌した。さらに５ｍｍＨｇの減圧下、１８０℃で２０時間撹拌した後、放冷したところ褐色のゴム状物が得られた。この分散剤１の酸価を測定したところ、１．５ｍｇＫＯＨ／ｇであった。また重量平均分子量は約４００，０００であった。
（２）水溶性ポリウレタン樹脂の非水分散重合
１０００ｍｌの４つ口セパラブルフラスコに、脱水したポリエチレングリコール（ＰＥＧ＃６０００、三洋化成工業品、OH価１２．８ｍｇＫＯＨ／ｇ）３００ｇ、２，６−ジーｔｅｒｔ−ブチルー４−メチルフェノール（ＢＨＴ、酸化防止剤）０．０５ｇを仕込み、反応器内にＮ2ガスを流しながら、攪拌機、温度計、冷却管を付ける。オイルバスにて８５℃に昇温し、ＰＥＧが溶解したら実施例１（１）で得たプレポリマーを９．８８ｇ、ＨＤＩを０．１５ｇ滴下ロートにて仕込み、攪拌混合する（ＰＥＧ：櫛形ジオール＝０．８５：０．１５、ＮＣＯ／ＯＨモル比＝１．０４）。８０℃に加温したイソオクタン３００ｇに上記分散剤１を１．５ｇ溶解させた溶液を反応器内にＮ2にて圧送した後、攪拌回転数を３００ｒｐｍまで上げ、８５℃で１時間撹拌し、分散させた。さらに、９０℃に昇温後、ジブチル錫ジラウレート（ＤＢＴＤＬ）触媒を０．０５ｇ添加し、６時間反応させて、溶剤中に分散した粒子状の水溶性ポリウレタン樹脂を得た。水溶性ポリウレタン樹脂の主粒子径は約９０〜５００μmで、重量平均分子量は約２８０，０００であった。
[Example 4]
-Synthesis of Dispersant 1 The acid value and polystyrene equivalent weight average molecular weight of polybutenyl succinic acid manufactured by Toho Chemical Co., Ltd. were measured. The acid value was 38.0 mgKOH / g, and the polystyrene equivalent weight average molecular weight was 3500. It was. 20.0 g of this and 10.0 g of polyethylene glycol 1000 (manufactured by Kanto Chemical Co., Inc.) were put into a 100 ml three-necked flask equipped with a stirring rod, and stirred at 180 ° C. for 20 hours under a nitrogen stream. The mixture was further stirred at 180 ° C. for 20 hours under a reduced pressure of 5 mmHg, and then allowed to cool to obtain a brown rubber-like product. The acid value of Dispersant 1 was measured and found to be 1.5 mgKOH / g. The weight average molecular weight was about 400,000.
(2) Non-aqueous dispersion polymerization of water-soluble polyurethane resin Into a 1000 ml four-necked separable flask, 300 g of dehydrated polyethylene glycol (PEG # 6000, Sanyo Chemical Industries, OH value 12.8 mgKOH / g), 2,6- Charge 0.05 g of tert-butyl-4-methylphenol (BHT, antioxidant) and add a stirrer, a thermometer and a cooling pipe while flowing N 2 gas into the reactor. When the temperature is raised to 85 ° C. in an oil bath and PEG is dissolved, 9.88 g of the prepolymer obtained in Example 1 (1) and 0.15 g of HDI are charged in a dropping funnel and mixed with stirring (PEG: comb-shaped diol) = 0.85: 0.15, NCO / OH molar ratio = 1.04). A solution prepared by dissolving 1.5 g of the dispersant 1 in 300 g of isooctane heated to 80 ° C. was pumped into the reactor with N 2 , and then the stirring rotation speed was increased to 300 rpm, followed by stirring at 85 ° C. for 1 hour. Dispersed. Furthermore, after raising the temperature to 90 ° C., 0.05 g of dibutyltin dilaurate (DBTDL) catalyst was added and reacted for 6 hours to obtain a particulate water-soluble polyurethane resin dispersed in a solvent. The main particle size of the water-soluble polyurethane resin was about 90 to 500 μm, and the weight average molecular weight was about 280,000.
［実施例５］
（１）分散剤２の合成
上記東邦化学（株）製のポリブテニルコハク酸を２０．０ｇ、ポリエチレングリコール１０００（関東化学製）１０．０ｇ、１，１０−デカンジオール０．５１ｇを撹拌棒付の１００ｍｌの3つ口フラスコに入れ、窒素気流下、１８０℃で２０時間撹拌した。さらに５ｍｍＨｇの減圧下、１８０℃で２０時間撹拌した後、放冷したところ褐色のゴム状物が得られた。この分散剤２の酸価を測定したところ、０．５ｍｇＫＯＨ／ｇであった。またポリスチレン換算重量平均分子量は３５０，０００であった。
（２）水溶性ポリウレタン樹脂の非水分散重合
実施例４における分散剤１を上記分散剤２に変更した以外は同様に非水分散重合反応を行った。得られた水溶性ポリウレタン樹脂の主粒子径は約９０〜５００μmで、重量平均分子量は約３４０，０００であった。
[Example 5]
(1) Synthesis of Dispersing Agent 2 20.0 g of polybutenyl succinic acid manufactured by Toho Chemical Co., Ltd., 10.0 g of polyethylene glycol 1000 (manufactured by Kanto Chemical), and 0.51 g of 1,10-decanediol were mixed with a stirring bar. The flask was placed in an attached 100 ml three-necked flask and stirred at 180 ° C. for 20 hours under a nitrogen stream. The mixture was further stirred at 180 ° C. for 20 hours under a reduced pressure of 5 mmHg, and then allowed to cool to obtain a brown rubber-like product. The acid value of Dispersant 2 was measured and found to be 0.5 mgKOH / g. The weight average molecular weight in terms of polystyrene was 350,000.
(2) Non-aqueous dispersion polymerization of water-soluble polyurethane resin A non-aqueous dispersion polymerization reaction was performed in the same manner except that the dispersant 1 in Example 4 was changed to the dispersant 2. The resulting water-soluble polyurethane resin had a main particle size of about 90 to 500 μm and a weight average molecular weight of about 340,000.
［実施例６］
水溶性ポリウレタン樹脂の非水分散重合
実施例４における分散剤１を荒川化学工業（株）製のアルキッド樹脂、アラキード７５０２Ｘ（OH価４０．０ｍｇＫＯＨ／ｇ、芳香族ジカルボン酸とペンタエリスリトールとのポリエステルを脂肪酸変性した樹脂）に変更し、さらに分散剤添加量を９．０ｇとした以外は同様に非水分散重合反応を行った。得られた水溶性ポリウレタン樹脂の主粒子径は約４００〜６００μmで、重量平均分子量は約１５０，０００であった。
[Example 6]
Non-aqueous dispersion polymerization of water-soluble polyurethane resin Dispersant 1 in Example 4 was used as an alkyd resin manufactured by Arakawa Chemical Industries, Arachid 7502X (OH value 40.0 mg KOH / g, polyester of aromatic dicarboxylic acid and pentaerythritol). A non-aqueous dispersion polymerization reaction was performed in the same manner except that the amount of the dispersant was changed to 9.0 g. The obtained water-soluble polyurethane resin had a main particle size of about 400 to 600 μm and a weight average molecular weight of about 150,000.
［実施例７］
（１）分散剤３の合成
平均分子量１０００のヘキサメチレンアジペートを２０ｇ、無水マレイン酸0.98ｇを撹拌棒付の１００ｍｌの3つ口フラスコに入れ、窒素気流下、１５０℃で２０時間撹拌した。さらに２０ｍｍＨｇの減圧下、１７０℃まで徐々に温度を上げて撹拌した後、放冷したところ平均分子量２０００の不飽和結合含有ポリオールが得られた。この不飽和結合含有ポリオール5ｇと、酢酸ブチル１０ｇを１００ｍｌナス型フラスコに入れ、窒素気流気化１１０℃で、ラウリルメタクリレート１０ｇと過酸化ベンゾイル０．４ｇを滴下ロートより３０分で滴下した。2時間１１０℃を保った後、１３０℃で２時間反応した。さらに、イソシアン酸エチル２ｇを加え、８０℃で６時間反応し、未反応物を5ｍｍＨｇで留去し、分散剤3を得た。この分散剤３のポリスチレン換算重量平均分子量は５３，０００であった。
（２）水溶性ポリウレタン樹脂の非水分散重合
実施例４における分散剤１を上記分散剤３に変更した以外は同様に非水分散重合反応を行った。得られた水溶性ポリウレタン樹脂の主粒子径は約９０〜５００μmで、重量平均分子量は約４００，０００であった。
[Example 7]
(1) Synthesis of Dispersant 3 20 g of hexamethylene adipate having an average molecular weight of 1000 and 0.98 g of maleic anhydride were placed in a 100 ml three-necked flask equipped with a stirrer and stirred at 150 ° C. for 20 hours under a nitrogen stream. Furthermore, under a reduced pressure of 20 mmHg, the temperature was gradually raised to 170 ° C. and the mixture was stirred and then allowed to cool to obtain an unsaturated bond-containing polyol having an average molecular weight of 2000. 5 g of this unsaturated bond-containing polyol and 10 g of butyl acetate were placed in a 100 ml eggplant type flask, and 10 g of lauryl methacrylate and 0.4 g of benzoyl peroxide were added dropwise from a dropping funnel in 30 minutes at a nitrogen stream vaporization of 110 ° C. After maintaining at 110 ° C. for 2 hours, the reaction was conducted at 130 ° C. for 2 hours. Furthermore, 2 g of ethyl isocyanate was added and reacted at 80 ° C. for 6 hours. Unreacted substances were distilled off at 5 mmHg to obtain Dispersant 3. This dispersant 3 had a polystyrene-reduced weight average molecular weight of 53,000.
(2) Non-aqueous dispersion polymerization of water-soluble polyurethane resin A non-aqueous dispersion polymerization reaction was performed in the same manner except that the dispersant 1 in Example 4 was changed to the dispersant 3. The obtained water-soluble polyurethane resin had a main particle size of about 90 to 500 μm and a weight average molecular weight of about 400,000.
［実施例８］
（１）分散剤４の合成
実施例7と同様に不飽和結合含有ポリオールを合成し、さらに、イソシアン酸エチル２ｇを加え、８０℃で６時間反応し、未反応物を5ｍｍＨｇで留去し、不飽和結合含有ポリエステルを得た。この不飽和結合含有ポリエステル5ｇと、酢酸ブチル１０ｇを１００ｍｌナス型フラスコに入れ、窒素気流気化１１０℃で、ラウリルメタクリレート１０ｇと過酸化ベンゾイル０．４ｇを滴下ロートより３０分で滴下した。2時間１１０℃を保った後、１３０℃で２時間反応し分散剤4を得た。この分散剤４のポリスチレン換算重量平均分子量は５５，０００であった。
（２）水溶性ポリウレタン樹脂の非水分散重合
実施例４における分散剤１を上記分散剤４に変更した以外は同様に非水分散重合反応を行った。得られた水溶性ポリウレタン樹脂の主粒子径は約９０〜５００μmで、重量平均分子量は約４５０，０００であった。
[Example 8]
(1) Synthesis of Dispersant 4 An unsaturated bond-containing polyol was synthesized in the same manner as in Example 7. Further, 2 g of ethyl isocyanate was added and reacted at 80 ° C. for 6 hours. Unreacted substances were distilled off at 5 mmHg. An unsaturated bond-containing polyester was obtained. 5 g of this unsaturated bond-containing polyester and 10 g of butyl acetate were placed in a 100 ml eggplant type flask, and 10 g of lauryl methacrylate and 0.4 g of benzoyl peroxide were added dropwise from the dropping funnel in 30 minutes at a nitrogen stream vaporization of 110 ° C. After maintaining at 110 ° C. for 2 hours, reaction was performed at 130 ° C. for 2 hours to obtain Dispersant 4. This dispersant 4 had a polystyrene-reduced weight average molecular weight of 55,000.
(2) Non-aqueous dispersion polymerization of water-soluble polyurethane resin A non-aqueous dispersion polymerization reaction was performed in the same manner except that the dispersant 1 in Example 4 was changed to the dispersant 4. The obtained water-soluble polyurethane resin had a main particle size of about 90 to 500 μm and a weight average molecular weight of about 450,000.
［実施例９］
・ 分散剤５の合成
上記分散剤２、２．７４ｇをトルエン３０ｍｌに溶解した。これにイソシアン酸エチル０．５０ｇ、ジブチル錫ジラウレート（ＤＢＴＤＬ）触媒０．０３ｇを加え、窒素気流下、８０℃で４時間撹拌した。トルエン、残イソシアン酸を減圧留去し、末端をマスキングした分散剤５、３．２０ｇを得た。
（２）水溶性ポリウレタン樹脂の非水分散重合
１０００ｍｌの４つ口セパラブルフラスコに、脱水したポリエチレングリコール（ＰＥＧ＃６０００、三洋化成工業品、OH価１２．８ｍｇＫＯＨ／ｇ）３００ｇ、２，６−ジーｔｅｒｔ−ブチルー４−メチルフェノール（ＢＨＴ、酸化防止剤）０．０５ｇを仕込み、反応器内にＮ2ガスを流しながら、攪拌機、温度計、冷却管を付ける。オイルバスにて８５℃に昇温し、ＰＥＧが溶解したら実施例１（１）で得たプレポリマーを９．８８ｇ、ＨＤＩを０．１５ｇ滴下ロートにて仕込み、攪拌混合する（ＰＥＧ：櫛形ジオール＝０．８５：０．１５、ＮＣＯ／ＯＨモル比＝１．０４）。８０℃に加温したイソオクタン３００ｇに上記分散剤５を１．５ｇ溶解させた溶液を反応器内にＮ2にて圧送した後、攪拌回転数を３００ｒｐｍまで上げ、８５℃で１時間撹拌し、分散させた。さらに、９０℃に昇温後、ジブチル錫ジラウレート（ＤＢＴＤＬ）触媒を０．０５ｇ添加し、６時間反応させて、溶剤中に分散した粒子状の水溶性ポリウレタン樹脂を得た。水溶性ポリウレタン樹脂の主粒子径は約９０〜３００μmで、重量平均分子量は約４３０，０００であった。
[Example 9]
-Synthesis of Dispersant 5 Dispersant 2,2.74 g was dissolved in 30 ml of toluene. To this were added 0.50 g of ethyl isocyanate and 0.03 g of dibutyltin dilaurate (DBTDL) catalyst, and the mixture was stirred at 80 ° C. for 4 hours under a nitrogen stream. Toluene and residual isocyanate were distilled off under reduced pressure to obtain 3.20 g of dispersant 5, whose ends were masked.
(2) Non-aqueous dispersion polymerization of water-soluble polyurethane resin Into a 1000 ml four-necked separable flask, 300 g of dehydrated polyethylene glycol (PEG # 6000, Sanyo Chemical Industries, OH value 12.8 mgKOH / g), 2,6- Charge 0.05 g of tert-butyl-4-methylphenol (BHT, antioxidant) and add a stirrer, a thermometer and a cooling pipe while flowing N 2 gas into the reactor. When the temperature is raised to 85 ° C. in an oil bath and PEG is dissolved, 9.88 g of the prepolymer obtained in Example 1 (1) and 0.15 g of HDI are charged in a dropping funnel and mixed with stirring (PEG: comb-shaped diol) = 0.85: 0.15, NCO / OH molar ratio = 1.04). A solution prepared by dissolving 1.5 g of the dispersant 5 in 300 g of isooctane heated to 80 ° C. was pumped into the reactor with N 2 , and then the stirring rotation speed was increased to 300 rpm, followed by stirring at 85 ° C. for 1 hour. Dispersed. Furthermore, after raising the temperature to 90 ° C., 0.05 g of dibutyltin dilaurate (DBTDL) catalyst was added and reacted for 6 hours to obtain a particulate water-soluble polyurethane resin dispersed in a solvent. The main particle diameter of the water-soluble polyurethane resin was about 90 to 300 μm, and the weight average molecular weight was about 430,000.
Claims (10)
〔ただし、ＡはＨＯ−Ａ−ＯＨが少なくとも両末端に水酸基を有しかつ数平均分子量が４００〜１００，０００の水溶性ポリオキシアルキレンポリオール（化合物Ａ）である２価基であり、該水溶性ポリオキシアルキレンポリオールが、エチレンオキサイドの重合物であり、ＢはＯＣＮ−Ｂ−ＮＣＯが全炭素数が３〜１８のポリイソシアナート類よりなる群から選ばれたポリイソシアナート化合物（化合物Ｂ）である２価基であり、ＤはＨＯ−Ｄ−ＯＨが化学式３（化３）
[However, A is a divalent group which is a water-soluble polyoxyalkylene polyol (compound A) having a hydroxyl group at both ends of HO-A-OH and a number average molecular weight of 400 to 100,000. Polyoxyalkylene polyol is a polymer of ethylene oxide, B is a polyisocyanate compound (compound B) selected from the group consisting of polyisocyanates having 3-18 carbon atoms in OCN-B-NCO Wherein D is HO—D—OH is represented by the chemical formula 3
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